CN1675381A - Formulation for use in chrome or chrome-free tannage - Google Patents
Formulation for use in chrome or chrome-free tannage Download PDFInfo
- Publication number
- CN1675381A CN1675381A CNA038195127A CN03819512A CN1675381A CN 1675381 A CN1675381 A CN 1675381A CN A038195127 A CNA038195127 A CN A038195127A CN 03819512 A CN03819512 A CN 03819512A CN 1675381 A CN1675381 A CN 1675381A
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- China
- Prior art keywords
- tanning
- tanning agent
- clay mineral
- chrome
- less
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000000203 mixture Substances 0.000 title abstract description 9
- 238000009472 formulation Methods 0.000 title abstract description 5
- 239000002734 clay mineral Substances 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 235000013311 vegetables Nutrition 0.000 claims abstract description 5
- 229920000620 organic polymer Polymers 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000049 pigment Substances 0.000 claims abstract description 3
- 239000011324 bead Substances 0.000 claims description 23
- 239000005995 Aluminium silicate Substances 0.000 claims description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims description 17
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 230000011218 segmentation Effects 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 150000003457 sulfones Chemical class 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical class O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 4
- 239000000020 Nitrocellulose Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- -1 ethylhexyl Chemical group 0.000 claims description 4
- 229910000271 hectorite Inorganic materials 0.000 claims description 4
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 229920001220 nitrocellulos Polymers 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 150000003672 ureas Chemical class 0.000 claims description 4
- 238000000149 argon plasma sintering Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 12
- 230000002902 bimodal effect Effects 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract 2
- 239000003086 colorant Substances 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 125000001174 sulfone group Chemical group 0.000 abstract 1
- 239000010985 leather Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 241000446313 Lamella Species 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 238000004049 embossing Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000283699 Bos indicus Species 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 210000000051 wattle Anatomy 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 1
- 102100031118 Catenin delta-2 Human genes 0.000 description 1
- 101000932768 Conus catus Alpha-conotoxin CIC Proteins 0.000 description 1
- 101000922056 Homo sapiens Catenin delta-2 Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 241000388430 Tara Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical group [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000000276 sedentary effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
Abstract
The invention relates to a formulation for use in chrome or chrome-free tannage. Said formulation comprises a clay mineral, which after 30 minutes of intense stirring in water at 50 DEG C has an average particle diameter of less than 2 m, or a bimodal size distribution consisting of a first fine-particle fraction, whose average particle diameter is less than 0.5 m and a second coarser fraction, whose average particle diameter is less than 5 m, said values being defined according to the ISO 13320-1 determination method by means of combined laser light diffraction and light diffusion, the proportion of the first fine-particle fraction lying between 10 and 90 wt. %. The formulation also comprises one or more substances from one or more of the following groups: organic polymers, aldehyde tanning agents, sulphone tanning agents, resin tanning agents, phenol tanning agents, stuffing agents, vegetable tanning agents, colorants and pigments.
Description
The present invention relates to be used for the batching of chrome-free tanning and chrome tanning, it comprises clay mineral, and the purposes that relates to clay mineral.
In tanning, putrefactive animal hides material is by carrying out preliminary treatment with the tanning auxiliary agent, processing with the chemical reaction of tanning agent and suitable arrangement, to be maintained soft and to have the resistance leather of desired properties (referring to R mpp Chemie Lexikon, the 9th edition, 1995, the 1538 pages).Thereby the high water content that is used to stablize the collagen structure of initial rawhide material is lowered, and irreversible stabilization is by realizing with tanning agent is crosslinked.Between inorganic, mineral and organic chemistry tanning agent, have any different.Inorganic tanning agent mainly is chromium (III) salt, polyphosphate and aluminium, zirconium and molysite.Organic tanning agent can be synthetic or plant origin (referring to R mpp Chemie Lexikon, the 9th edition, 1995, the 1541 pages).
Known that inorganic polymer is general as filler in tanning.According to H.Herfeld:Bibliothek des Leders, the 3rd volume, Umschau Verlag, Frankfurt, the 2nd edition, 1990,227 pages description, mineral filler do not have the tanning effect.These fillers comprise kaolin, segmentation clay (potter's clay), colloidal silica etc.These products be deposited in the major portion of open structure and preferred deposition at flesh noodles.Influence to the grain structure is very little, and the property softened (buffability) is improved usually, and lint is shorter.
But shortcoming is that introduce on combination or surface very loose in the rawhide material.So in the processing step subsequently of leather production for example ground, the material that is introduced into of significant proportion was discharged once more, cause grain to stop up or to the wear damage of grain structure.
DE-C 969689 has described silicon-dioxide and/or the silicate that uses the filler, particularly colloidal form that contain surfactivity silicon, has the granularity of 0.1-1 micron, is used to flatten, shorten and the particularly softening surface of leather that becomes more meticulous.These siliceous colloid dirt tend to be adsorbed on the collegen filament by force, even the result is during subsequent operations, the introducing of material is also kept basically.But the shortcoming of colloidal silica, silicate or its mixture is to stand successive as dynamic system to change.In this change process, because the Ostwald slaking, the initial particle generation size of introducing occurring in the storage of leather/leatherware or use increases, and obtains the aggregation of sand shape.As a result, for example in rotary drum processing, cause the wearing and tearing of leather in the walking wrinkle at the upper strata leather.So think that this silicate tanning is unsettled relatively.
Y.Lakshminarayana etc. are at JALCA 97 (2002), and the technical article among the 14-21 has been described wilkinite and has been used to prepare graftomer with methacrylic acid, is used for tanning, especially for the aftertreatment of chrome tanning leather.
The purpose of this invention is to provide a kind of stable batching that comprises clay that is used for chrome-free tanning and chrome tanning, this batching is guaranteed from the improvement performance of the leather of its acquisition and technologic improvement.
We find that this purpose can realize by the batching that is used for chrome-free tanning and chrome tanning, these ingredient bags argillaceous mineral, its 50 ℃ in water vigorous stirring have number average bead diameter after 30 minutes less than 2 microns, or has a bomodal size distribution, wherein the number average bead diameter of the first segmentation fraction is less than 0.5 micron, the number average bead diameter of the second thick fraction is less than 5 microns, this is in all cases by laser diffraction and the determination of light scattering of method by making up according to ISO13320-1, the amount of the first segmentation fraction is 10-90 weight %, this batching also contains one or more and is selected from following material: organic polymer, aldehyde tanning agent, the sulfone tanning agent, resin tanning agent, the phenol tanning agent, fatting agent, vegetable tanning agent, dyestuff and pigment.
Be surprised to find and used such clay mineral as tanning agent or be used to prepare tanning agent and can make the performance of leather by its acquisition significantly improve, wherein this clay mineral in warm water by having number average bead diameter after the vigorous stirring layering less than 2 microns, or has a bomodal size distribution, wherein the number average bead diameter of the first segmentation fraction is less than 0.5 micron, the number average bead diameter of the second thick fraction is less than 5 microns, and the amount of the described first segmentation fraction is 10-90 weight %.For layering to determine number average bead diameter, need handle with capacity, the about 950ml water that generally is based on the 50g clay mineral for example stirs under 250rpm 50 ℃ of vigorous stirring 30 minutes, its CLAY MINERALS AND THEIR SIGNIFICANCE is dispersed in the water.This processing intended to ensure clay mineral carries out layering and no longer changes up to granularity.
Granularity and size-grade distribution are Malvern 2000 analytical instrument of using Malvern company by the laser diffraction and the scattering of light of combination according to ISO 13320-1.
Think that the interaction between the collagen chain of clay mineral and rawhide is necessary for the effect of the clay mineral with above-mentioned granularity.This interaction is possible by the hydrogen bridge between the surface hydroxyl of collagen and clay mineral for example.Being surprised to find the clay mineral with above-mentioned granularity is irreversibly introduced in the rawhide.
Clay mineral is the sedentary product of main silico-aluminate, promptly contains the aluminum oxide of different ratios and the formulation of silicon-dioxide.Silicon is surrounded in the tetrahedron mode by four Sauerstoffatoms, and aluminium is present in octahedral coordination.Clay mineral mainly belongs to phyllosilicate, is also referred to as sheet silicate or layered silicate, but is also referred to as banded silicate (referring to R mpp Chemie Lexikon, the 9th edition, 1995,4651-4652 page or leaf) in some cases.
For new batching,, then be particularly advantageous if clay mineral is a phyllosilicate.Phyllosilicate is kaolin, white mica, polynite, terre verte or wilkinite, particularly hectorite preferably.If the material that will be owing to its chemical structure can form strong hydrogen bridge band with clay mineral its as before the tanning agent or during add in the clay mineral, then obtain good especially result, described material is urea or urea derivatives, alcohol, polyvalent alcohol, Texacar PC, organic amide, carbamate, sugar or sugared derivative, especially Nitrocellulose, sulfite cellulose or ethylhexyl Mierocrystalline cellulose particularly.By this processing, the layering of clay mineral, particularly sheet silicate obtains promoting.
The organic polymer that can use in new batching is for example polymethacrylate, polyacrylic ester, maleic anhydride/styrol copolymer or maleic anhydride/isobutylene copolymers.
The number average bead diameter of preferred its CLAY MINERALS AND THEIR SIGNIFICANCE is less than 1 micron batching.
Such batching is specially suitable, these ingredient bags argillaceous mineral, this clay mineral 50 ℃ in water vigorous stirring have number average bead diameter after 30 minutes less than 2 microns, or has a bomodal size distribution, wherein the number average bead diameter of the first segmentation fraction is less than 0.5 micron, the number average bead diameter of the second thick fraction is less than 5 microns, this is according to laser diffraction and the determination of light scattering of method by making up of ISO 13320-1, the amount of the first segmentation fraction is 10-90 weight %, with aldehyde tanning agent be the derivative of glutaraldehyde or glutaraldehyde, particularly acetal.
The invention still further relates to clay mineral as tanning agent or be used to prepare the purposes of tanning agent, this clay mineral 50 ℃ in water vigorous stirring have number average bead diameter after 30 minutes less than 2 microns, or has a bomodal size distribution, wherein the number average bead diameter of the first segmentation fraction is less than 0.5 micron, the number average bead diameter of the second thick fraction is less than 5 microns, and the amount of the first segmentation fraction is 10-90 weight %.
The preferred number average bead diameter of using is less than 1 micron clay mineral.
Such purposes is preferred, the material that wherein will be can form strong hydrogen bridge band with clay mineral owing to its chemical structure clay mineral as before the tanning agent or during be added in the clay mineral, described material is urea or urea derivatives, alcohol, polyvalent alcohol, Texacar PC, organic amide, carbamate, sugar or sugared derivative, especially Nitrocellulose, sulfite cellulose or ethylhexyl Mierocrystalline cellulose particularly.
The preferred clay mineral that uses is a phyllosilicate, preferred especially kaolin, white mica, polynite, terre verte or wilkinite, particularly hectorite.
Described clay mineral is preferably as tanning agent or be used to prepare the tanning agent that the elementary tanning of elementary tanning, particularly Chrome-free is used.
Further preferably its CLAY MINERALS AND THEIR SIGNIFICANCE is as tanning agent or be used to prepare the chrome tanning that retanning uses or the tanning agent of chrome-free tanning.
Following advantage realizes by described new batching and new purposes:
Particularly, realized significantly improved selectivity filling effect, promptly loose zone preferably is filled, and the result is that leather quality and surperficial yield are improved.
The grain density is significantly improved, and promptly wrinkle from the teeth outwards or cracking significantly reduce or be avoided.
The leather quality also is improved by improved embossability.
In addition, the leather quality is improved by the raising of tensile strength.
In the early stage in the tanning, particularly an important qualitative characteristics under Chrome-free leather situation is half-finished lamella.This is improved by the present invention, causes the uniform thickness of rawhide behind improved surface property and the sheet and the tool wear, particularly tool wear that reduces in the lamella process.Because the binding property of the cutter that lamella is used reduces, processibility is improved, thereby the time of saving also is significant.
According to the present invention, natural fat distribution with the fat that applies is improved, and obtains more all even more regular surface.In addition, the inhomogeneity improvement of this fat distribution makes might save fatting agent up to 50% in retanning, thereby provides especially and the process for tanning of environmentally compatible, has quite low contaminated wastewater.
Remarkable advantage of the present invention is that the consistency of and environment feasible by liquid-consumed (liquor exhaustion), particularly fatting agent aspect obtains the remarkable improvement up to 50%, has corresponding lower contaminated wastewater.
Describe the present invention in detail below with reference to embodiment.
The initial stage tanning of the wet white skin of embodiment E 1.1 to 1.4 and Comparative Examples C1.0 to 1.4
The commercial grade of following trade(brand)name is the product of BASFAG (Ludwigshafen).
It is 1.6-1.8mm that riem after the acidleach is divided into thickness, 250g respectively weighs, handled 60 minutes with 3% glutaraldehyde water solution (Relugan GT24) continuously at 25 ℃ and pH3.0 with 200g water in each case, then with 4% sulfone tanning agent Basyntan SW processing.After time, pH is brought up to 3.8-4.0 at 90 minutes rotary drums with the Tamol NA and the sodium formiate of 2 weight parts.
In Comparative Examples C1 to C1.4 and embodiment 1.1 to 1.4, the 10g clay mineral described in the following table 1 is added in the liquid with glutaraldehyde solution in all cases.The mean particle size of clay mineral is by being that 5% freshly prepd suspension carries out laser diffraction/scattering of light and measures according to ISO 13320-1 to solid content in all cases.
In the early stage after the tanning, in all cases, with the strainer coarse filtration of each liquid of 100g by 25 microns.Remaining solid content precipitates in centrifugal, and washing is dry and weigh then.
Following table 1 has shown the solid content of the liquid after tannery, in all cases based on initial total liquid.The lamella of the leather of process initial stage tanning is estimated according to grade 1-5.Shrinkage temperature is measured according to DIN 53336, and youngster's point improves it below:
Point 4.1: the size of sample is 3cm1cm, and thickness is not measured;
Point 4.2: replace two samples, only for sample of each leather sample detection;
Point 6: omit;
Point 7: omitted under reduced pressure the drying in moisture eliminator and
Point 8: when the pointer travelling backwards, read shrinkage temperature.
Table 1
| Clay mineral | Median size [micron] | The solid content of liquid [g] | Lamella [grade 1-5] | Shrinkage temperature [℃] | |
| ????C?1.0 | ??- | ????- | ????- | ????3 | ????79 |
| ????C?1.1 | Kaolin | ????13.2 | ????3.8 | ????3.5 | ????77 |
| ????C?1.2 | Kaolin | ????7.6 | ????2.9 | ????3 | ????78 |
| ????C?1.3 | Kaolin | ????5.1 | ????2.7 | ????2.5 | ????78 |
| ????C?1.4 | Kaolin | ????3.2 | ????1.4 | ????2.5 | ????79 |
| ????E?1.1 | Kaolin | ????1.3 | ????0.55 | ????1.5 | ????81 |
| ????E?1.2 | Polynite | ????0.6 | ????0.30 | ????1 | ????83 |
| ????E?1.3 | Kaolin/polynite | Bimodal 0.6/3.2 | ????0.7 | ????1 | ????82 |
| ????E?1.4 | Kaolin/wilkinite | ????0.2/1.3 | ????0.35 | ????1 | ????82 |
The tannery liquid solid content afterwards that relatively is presented at of Comparative Examples C1.0 to 1.4 and embodiment of the invention E1.1 to 1.4 significantly reduces (the 4th row of table 1), be liquid-consumed being significantly improved, and lamella (the 5th row) and shrinkage temperature (last row) are improved.
The retanning of the blue wet upper strata of Comparative Examples C2.0 and C2.1 and embodiment E 2.1 and E2.2 skin
It is 1.8-2.0mm that industrial Zebu wet blue is divided into thickness, and is divided into four parts.Then, the Tamol NA of the sodium bicarbonate of 2% sodium formiate and 0.4% and 1% is added in each part in the rotary drum, liquid length is 200%, and promptly every 1kg leather has the 2kg aqueous phase liquid, interval 10 minutes.After 90 minutes, expel liquid, each part of Zebu are distributed in four drums.
In Comparative Examples 2.0,1% aqueous solution that dyestuff Luganil is brown is metered in the drum at 25 ℃, Zebu part is carried out rotary drum handled 10 minutes.
Then, add 3% Polymer Tanning Agent Relugan RV, 5% sulfone tanning agent Basyntan DLX and 2% resin tanning agent Relugan DLF, and under 10rpm, carry out rotary drum processing 20 minutes once more.
Then, rawhide was handled 40 minutes with 3% industrial wattle vegetable tanning agent, and then handled 40 minutes with 2% wattle vegetable tanning agent.
Carry out acidifying with formic acid then, reaching pH is 3.6-3.8.After 20 minutes, expel liquid is used 200% water washing.At last, at 50 ℃ 5% Lipodermlicker CMG and 2% Lipodermlicker PN are metered in 100% water.After rotary drum processing 45 minutes, carry out acidifying with 1% formic acid.
Leather after the washing carry out drying and draw soft, and aspect the homogeneity of fullness ratio, grain density, pliability and dyeing/stuffing according to the evaluation system evaluation quality of 1 (very good)-5 (being unsatisfied with).In addition, measure in newton's tensile strength with according to anti-pin the tearing property of DIN53331 measurement according to DIN 53328 in newton.For the value of chemical oxygen demand (COD) relatively confirmed improved liquid-consumed amount with new clay mineral.
With in the comparison of Comparative Examples 2.0, in Comparative Examples 2.1, corresponding to the clay mineral of Comparative Examples 1.1, be that further granularity is that 13.2 microns kaolin is metered into sulfone tanning agent Basyntan DLX with 4% concentration.
In order to contrast, in all cases, in embodiment E 2.1 and E2.2, be metered into corresponding to 4% clay mineral of embodiment E 1.1 and E1.4.
Following table 2 has shown with Comparative Examples C2.0 to be compared with C2.1, and the leather that obtains in embodiment of the invention E2.1 and E2.2 has significant quality-improving at aspect the homogeneity of fullness ratio, grain density, pliability and dyeing/stuffing and tensile strength and anti-tearing property of pin aspect.
Table 2
| Clay mineral | Fullness ratio | The grain density | Pliability | Tensile strength [N] | Anti-tearing property of pin [N] | The homogeneity of dyeing/stuffing | COD [mgO 2/ l liquid] | |
| ??C?2.0 | ??- | ????3 | ????3.5 | ??3 | ??428 | ??302 | ??3 | ??16?200 |
| ??C?2.1 | ??C?1.1 | ????3 | ????3 | ??3.5 | ??410 | ??292 | ??2.5 | ??14?800 |
| ??E?2.1 | ??E?1.1 | ????2 | ????2.5 | ??2 | ??452 | ??319 | ??1 | ??10?700 |
| ??E?2.2 | ??E?1.4 | ????1.5 | ????2 | ??2.5 | ??449 | ??328 | ??1.5 | ??6?900 |
The retanning of the wet white upholstery leather of Comparative Examples C3.0-C3.2 and embodiment 3.1-3.3
The southern German ox-hide is changed into wet white work in-process, and it is 1.2mm that sheet becomes thickness, and is divided into the bar of each about 250g.
In Comparative Examples 3.0, rawhide was handled 40 minutes at 35 ℃ with 150% water that contains 3%Relugan GT50 (batching that promptly contains glutaraldehyde water solution substantially) and 0.5% formic acid.Then, the Tamol NA of usefulness equal portions and 4% mixture process of sodium formiate 60 minutes use 4% Relugan SE and 5%Basyntan SW (being the sulfone tanning agent) to carry out rotary drum processing 20 minutes then.Then, industrial plant tanning agent Tara with 6% and 2% resin tanning agent Relugan S and 2% the brown NGB of dyestuff Luganil are metered into, and this mixture is carried out rotary drum processing once more.After 2 hours, making pH with formic acid is 3.6.The stuffing component that adds is 6% Lipodermlicker CMG and 1% Lipodermlicker OK.After rotary drum processing 60 minutes, carry out acidifying with formic acid once more, reach pH and be 3.2 and before expel liquid, the solid content of working sample, promptly liquid-consumed amount.Each with 100% water washing leather, carry out twice, in the hygrometric state store overnight, after the part drying, in 50 ℃ stretching tight the joint clamp stand on drying.
According to the evaluation system evaluation liquid consumption of 1 (very good)-5 (being unsatisfied with) with at the leather quality aspect fullness ratio, grain density, pliability, homogeneity and the embossing.The evaluation of liquid-consumed amount is estimated according to the standard of residual dye (minimizing) and haziness (fatting agent).In order to estimate embossing, skin bit is handled according to following operation: put in order and suppressed 5 seconds with platen press 120 crust and 80-100 ℃.The quality of embossing is according to the standard evaluation of the embossing degree of depth, homogeneity and the memory after tension load.
In Comparative Examples C3.0, do not add clay mineral, in Comparative Examples C3.1, add clay mineral corresponding to Comparative Examples C1.1, the kaolin that promptly has 13.2 microns mean particle sizes, with the clay mineral that in Comparative Examples C3.2, adds corresponding to Comparative Examples C1.3, the kaolin that promptly has 5.1 microns mean particle sizes.
In embodiment E 3.1, add clay mineral corresponding to embodiment E 1.1, the kaolin that promptly has 1.3 microns mean particle sizes, in embodiment E 3.2, add clay mineral corresponding to embodiment E 1.2, the polynite that promptly has 0.6 micron mean particle size, with the clay mineral that in embodiment E 3.3, adds corresponding to embodiment E 1.3, promptly have the kaolin of bimodal mean particle size and the mixture of polynite, one of them fraction has 0.6 micron mean particle size, and second fraction has 3.2 microns mean particle size.
Table 3
| Clay mineral | Liquid-consumed | Fullness ratio | The grain density | Pliability | Tensile strength [N] | Anti-tearing property of pin [N] | Homogeneity | Embossing | |
| ?C?3.0 | ?- | ??3.0 | ????3 | ??3.5 | ????3 | ??268 | ??192 | ????3 | ????3 |
| ?C?3.1 | ?C?1.1 | ??4 | ????3 | ??3 | ????3.5 | ??248 | ??188 | ????2.5 | ????3.5 |
| ?C?3.2 | ?C?1.3 | ??3.5 | ????2.5 | ??2.5 | ????3 | ??259 | ??194 | ????2 | ????3 |
| ?E?3.1 | ?E?1.1 | ??2.5 | ????2 | ??2.5 | ????2 | ??277 | ??201 | ????1 | ????2.5 |
| ?E?3.2 | ?E?1.2 | ??2 | ????2 | ??1.5 | ????2 | ??284 | ??223 | ????1 | ????1.5 |
| ?E?3.3 | ?E?1.3 | ??1.5 | ????1.5 | ??2 | ????2.5 | ??289 | ??218 | ????1.5 | ????1.5 |
The improvement that relatively shows all qualitative characteristicss of Comparative Examples C3.0-C3.2 and embodiment of the invention E3.1 to E3.3 in the table 3, i.e. fullness ratio, grain density, pliability, tensile strength, anti-tearing property of pin, homogeneity, embossing and liquid-consumed.
Claims (13)
1, a kind of batching that is used for chrome-free tanning and chrome tanning, these ingredient bags argillaceous mineral, its 50 ℃ in water vigorous stirring have number average bead diameter after 30 minutes less than 2 microns, or has a bomodal size distribution, wherein the number average bead diameter of the first segmentation fraction is less than 0.5 micron, the number average bead diameter of the second thick fraction is less than 5 microns, this is in all cases by the method according to ISO 13320-1, laser diffraction and determination of light scattering by combination, the amount of the first segmentation fraction is 10-90 weight %, this batching also contains one or more and is selected from following material: organic polymer, aldehyde tanning agent, the sulfone tanning agent, resin tanning agent, the phenol tanning agent, fatting agent, vegetable tanning agent, dyestuff and pigment.
2, according to the batching of claim 1, wherein aldehyde tanning agent is the derivative of glutaraldehyde or glutaraldehyde, particularly acetal.
3, according to the batching of claim 1 or 2, the number average bead diameter of its CLAY MINERALS AND THEIR SIGNIFICANCE is less than 1 micron.
4, according to each batching of claim 1-3, the material that wherein will be can form strong hydrogen bridge band with clay mineral owing to its chemical structure clay mineral as before the tanning agent or during add in the clay mineral, described material is urea or urea derivatives, alcohol, polyvalent alcohol, Texacar PC, organic amide, carbamate, sugar or sugared derivative, especially Nitrocellulose, sulfite cellulose or ethylhexyl Mierocrystalline cellulose particularly.
5, according to each batching of claim 1-4, its CLAY MINERALS AND THEIR SIGNIFICANCE is a phyllosilicate.
6, according to each batching of claim 1-5, wherein phyllosilicate is kaolin, white mica, polynite, terre verte or wilkinite, particularly hectorite.
7, clay mineral is as tanning agent or be used to prepare the purposes of tanning agent, this clay mineral 50 ℃ in water vigorous stirring have number average bead diameter after 30 minutes less than 2 microns, or has a bomodal size distribution, wherein the number average bead diameter of the first segmentation fraction is less than 0.5 micron, the number average bead diameter of the second thick fraction is less than 5 microns, and the amount of the first segmentation fraction is 10-90 weight %.
8, according to the purposes of claim 7, the number average bead diameter of its CLAY MINERALS AND THEIR SIGNIFICANCE is less than 1 micron.
9, according to the purposes of claim 7 or 8, the material that wherein will be can form strong hydrogen bridge band with clay mineral owing to its chemical structure clay mineral as before the tanning agent or during add in the clay mineral, described material is urea or urea derivatives, alcohol, polyvalent alcohol, Texacar PC, organic amide, carbamate, sugar or sugared derivative, especially Nitrocellulose, sulfite cellulose or ethylhexyl Mierocrystalline cellulose particularly.
10, according to each purposes of claim 7-9, its CLAY MINERALS AND THEIR SIGNIFICANCE is a phyllosilicate.
11, according to the purposes of claim 10, wherein phyllosilicate is kaolin, white mica, polynite, terre verte or wilkinite, particularly hectorite.
12, according to each purposes of claim 7-11, the tanning agent that its CLAY MINERALS AND THEIR SIGNIFICANCE is used as elementary tanning or be used to prepare the tanning agent that the elementary tanning of elementary tanning, particularly Chrome-free is used.
13, according to each purposes of claim 7-11, the tanning agent that its CLAY MINERALS AND THEIR SIGNIFICANCE is used as retanning or be used to prepares the chrome tanning that retanning uses or the tanning agent of chrome-free tanning.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10237259.4 | 2002-08-14 | ||
| DE10237259A DE10237259A1 (en) | 2002-08-14 | 2002-08-14 | Clay mineral giving specified particle size on stirring in water is used as a leather tanning agent, especially in combination with an organic tanning agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1675381A true CN1675381A (en) | 2005-09-28 |
| CN100363507C CN100363507C (en) | 2008-01-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038195127A Expired - Fee Related CN100363507C (en) | 2002-08-14 | 2003-08-08 | Formulation for use in chrome or chrome-free tannage |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US7771489B2 (en) |
| EP (1) | EP1530647B1 (en) |
| KR (1) | KR20050053609A (en) |
| CN (1) | CN100363507C (en) |
| AR (1) | AR040862A1 (en) |
| AT (1) | ATE426683T1 (en) |
| AU (1) | AU2003260394A1 (en) |
| BR (1) | BR0313072A (en) |
| DE (2) | DE10237259A1 (en) |
| WO (1) | WO2004022790A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586504A (en) * | 2011-12-20 | 2012-07-18 | 河北东明皮革有限公司 | Sheepskin tanning technology |
| CN103014192A (en) * | 2012-12-28 | 2013-04-03 | 陕西科技大学 | Method for preparing flame-retardant nano-composite fatting agent by fatty acid modified montmorillonoid |
| CN103060488A (en) * | 2012-12-26 | 2013-04-24 | 四川亭江新材料股份有限公司 | Environment-friendly type crust leather production method |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10255095A1 (en) | 2002-11-26 | 2004-06-03 | Basf Ag | Process for the manufacture of a semi-finished leather product |
| MX2010012544A (en) * | 2008-05-16 | 2011-03-15 | Midori Hokuyo Co Ltd | Topcoat. |
| CN101509046B (en) * | 2009-03-19 | 2012-05-23 | 陕西科技大学 | Method of preparing environment friendly incrassation type nano-composite tanning agent for leather |
| GB201306607D0 (en) | 2013-04-11 | 2013-05-29 | Xeros Ltd | Method for treating an animal substrate |
| GB201417487D0 (en) | 2014-10-03 | 2014-11-19 | Xeros Ltd | Method for treating an animal substrate |
| GB201418006D0 (en) | 2014-10-10 | 2014-11-26 | Xeros Ltd | Animal skin substrate treatment apparatus and method |
| GB201418007D0 (en) | 2014-10-10 | 2014-11-26 | Xeros Ltd | Animal skin substrate Treatment apparatus and method |
| KR101518466B1 (en) * | 2014-12-29 | 2015-05-11 | (주)신도레더 | Manufacturing Method of Leather for Sofa |
| KR101518467B1 (en) * | 2014-12-30 | 2015-05-11 | (주)신도레더 | Leather for Sofa |
| PT3059327T (en) * | 2015-02-19 | 2017-11-16 | Taminco Finland Oy | An environmentally friendly chrome-tanning method |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE969689C (en) | 1953-02-27 | 1958-07-03 | Bayer Ag | Process for improving the sandability of leathers, in particular suede leathers |
| IT590719A (en) | 1957-05-17 | 1900-01-01 | ||
| US2992936A (en) * | 1958-11-21 | 1961-07-18 | Georgia Kaolin Co | Clay products and methods of producing them |
| US3719514A (en) * | 1967-11-24 | 1973-03-06 | Staley Mfg Co A E | Starch binder composition |
| US4272242A (en) * | 1977-07-16 | 1981-06-09 | Henkel Kommanditgesellschaft Auf Aktien | Use of water-insoluble aluminosilicates in tanning process for the production of leather |
| DE3704465C2 (en) * | 1987-02-13 | 1995-11-02 | Roehm Gmbh | Liquid formulations of enzymes |
| PL323618A1 (en) * | 1996-12-20 | 1998-06-22 | Tfl Ledertechnik Gmbh & Co Kg | Hide processing compositions |
| KR100818964B1 (en) * | 2000-09-21 | 2008-04-04 | 롬 앤드 하스 캄파니 | Aqueous nanocomposite dispersions: processes, compositions, and uses thereof |
| BR0206737A (en) * | 2001-01-30 | 2004-02-03 | Procter & Gamble | Coating compositions for surface modification |
| CN1143868C (en) | 2001-10-26 | 2004-03-31 | 中国科学院长春应用化学研究所 | In-situ emulsion polymerization process of preparing nano composite polyacrylate/clay material |
-
2002
- 2002-08-14 DE DE10237259A patent/DE10237259A1/en not_active Withdrawn
-
2003
- 2003-08-08 AU AU2003260394A patent/AU2003260394A1/en not_active Abandoned
- 2003-08-08 BR BRPI0313072-0A patent/BR0313072A/en not_active IP Right Cessation
- 2003-08-08 EP EP03793708A patent/EP1530647B1/en not_active Expired - Lifetime
- 2003-08-08 AT AT03793708T patent/ATE426683T1/en not_active IP Right Cessation
- 2003-08-08 CN CNB038195127A patent/CN100363507C/en not_active Expired - Fee Related
- 2003-08-08 DE DE50311346T patent/DE50311346D1/en not_active Expired - Lifetime
- 2003-08-08 KR KR1020057002374A patent/KR20050053609A/en not_active Application Discontinuation
- 2003-08-08 US US10/524,047 patent/US7771489B2/en not_active Expired - Fee Related
- 2003-08-08 WO PCT/EP2003/008830 patent/WO2004022790A1/en active Search and Examination
- 2003-08-13 AR AR20030102922A patent/AR040862A1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586504A (en) * | 2011-12-20 | 2012-07-18 | 河北东明皮革有限公司 | Sheepskin tanning technology |
| CN103060488A (en) * | 2012-12-26 | 2013-04-24 | 四川亭江新材料股份有限公司 | Environment-friendly type crust leather production method |
| CN103014192A (en) * | 2012-12-28 | 2013-04-03 | 陕西科技大学 | Method for preparing flame-retardant nano-composite fatting agent by fatty acid modified montmorillonoid |
Also Published As
| Publication number | Publication date |
|---|---|
| AR040862A1 (en) | 2005-04-20 |
| ATE426683T1 (en) | 2009-04-15 |
| US7771489B2 (en) | 2010-08-10 |
| EP1530647B1 (en) | 2009-03-25 |
| US20060101584A1 (en) | 2006-05-18 |
| AU2003260394A1 (en) | 2004-03-29 |
| BR0313072A (en) | 2007-07-17 |
| EP1530647A1 (en) | 2005-05-18 |
| WO2004022790A1 (en) | 2004-03-18 |
| DE10237259A1 (en) | 2004-02-26 |
| DE50311346D1 (en) | 2009-05-07 |
| CN100363507C (en) | 2008-01-23 |
| KR20050053609A (en) | 2005-06-08 |
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